KR20220120900A - Flexible environmentally friendly adhesive film - Google Patents

Abstract

The present invention relates to a Soft eco-friendly adhesive film, prepared by extruding an elastomer made of a PBT resin and a PET copolymer into a sheet or film form and applying an adhesive to a surface thereof. The present invention can be used for general purposes such as advertising, furniture, stationery, crafts, tapes, etc, and provide excellent processability, adhesiveness, printability, weatherability, and better heat resistance and cold resistance than PVC resin to be used in from rapidly growing interior materials for buildings and ships to exterior materials for automobiles, wallpaper, and adhesive tapes. The present invention can completely replace the soft PVC adhesive film that causes harmful substances to the human body or environmental problems.

Description

Flexible environmentally friendly adhesive film

The present invention relates to a soft eco-friendly adhesive film that can replace the soft PVC adhesive film, and more particularly, it is composed of an elastomer using PBT resin and PET copolymer resin as a base resin, so that it has heat resistance, cold resistance, weather resistance, adhesiveness, and printability. , relates to a soft eco-friendly adhesive film with excellent processability.

In general, the raw material of the flexible plastic adhesive film is mainly used soft PVC. Soft PVC resin has excellent properties such as tensile strength, elongation, and elasticity, as well as processability, price competitiveness, printability, and adhesiveness. ·The flexible PVC adhesive film used for bonding cannot be recycled due to the adhesive applied on the surface of the flexible PVC film and it is not easy to separate from the adherend, so most are incinerated together with the adherend. , olefin-based elastomers can be completely incinerated at a relatively low temperature of 600°C to 700°C, but PVC resin must be separately incinerated at a high temperature of 1,200°C or higher due to dioxin generated during incineration due to its high chlorine content. As a result, economic costs and environmental problems are increasing.

In addition, the occurrence of dioxin due to the high chlorine content of PVC resin is harmful to the human body and causes serious environmental problems. Due to its characteristics, poor weather resistance, adhesion, printability, and price competitiveness compared to PVC resin, it is still not completely replaced by eco-friendly plastics.

As the technology that is the background of the present invention, there is Patent Registration No. 1004614 "Deco sheet for PTV molding having a moldability similar to PVC" (Patent Document 1). In the background art, 'a PETG alloy resin obtained by melting and mixing an elastomer resin with a polyethylene terephthalate glycol (PETG) resin is included, and the elastomer resin is added to a polybutylene terephthalate (PBT) resin. We propose a decor sheet, characterized in that it is an elastomer resin copolymerized with polyether glycol.'

However, the background technology has a moldability similar to that of PVC, but is mainly used for hard sheets and food containers.

Patent Registration No. 1004614 "Deco sheet for PTV molding with moldability similar to PVC"

The present invention is to solve the above problems, and has excellent processability, adhesion, printability and heat resistance, cold resistance, and weather resistance than soft PVC resin by using an elastomer using PBT resin and PET copolymer as the base resin. Hardness can be arbitrarily adjusted from hardness 100 to A hardness of 80, so various adhesive tapes made of flexible PVC, wallpaper, interior and exterior flyers, adhesive films for automobiles and ships, stationery, crafts, etc. An object of the present invention is to provide a soft eco-friendly adhesive film that can be substituted for the adhesive film in the products of the company.

The present invention is to provide a soft eco-friendly adhesive film, characterized in that it is formed by extruding an elastomer using a PBT resin and a PET copolymer as a base resin into a sheet or film state, and applying an adhesive or an adhesive to the surface.

In addition, the elastomer is made by mixing 30 parts by weight to 320 parts by weight of an eco-friendly plasticizer and 50 parts by weight to 550 parts by weight of a TPEE (Thermoplastic copolyester elastomer) resin with respect to 100 parts by weight of the PBT resin. do.

In addition, the PBT resin is intended to provide a soft eco-friendly adhesive film characterized in that 30% to 100% by weight is replaced with a PET copolymer resin.

In addition, it is intended to provide a soft eco-friendly adhesive film characterized in that 15 to 160 parts by weight of an acrylic rubber copolymer or a butadiene rubber copolymer is mixed with respect to 100 parts by weight of the PBT resin.

In addition, to provide a soft eco-friendly adhesive film characterized in that the acrylic rubber copolymer or butadiene rubber copolymer is mixed with 15 parts by weight to 160 parts by weight of the styrenic block copolymer with respect to 100 parts by weight of the PBT resin. do.

In addition, the elastomer is intended to provide a soft eco-friendly adhesive film, characterized in that the hardness (hardness) A80 ± 3 ~ 100 ± 3.

The flexible environmetally adhesive film composed of the PBT resin and the PET copolymer of the present invention is a PVC resin with excellent processability, adhesion, printability, weather resistance, as well as general uses such as advertising, furniture, stationery, crafts, and tape. It is a very useful material that can completely replace the PVC flexible adhesive film that causes harmful substances to the human body and environmental problems, including interior materials for buildings and ships, automobile exterior materials, wallpaper, and adhesive tapes, which are rapidly increasing with better heat resistance and cold resistance. It works.

Hereinafter, the present invention will be described in detail with reference to the presented examples, but the presented examples are illustrative for a clear understanding of the present invention, and the present invention is not limited thereto.

Hereinafter, the technical configuration of the present invention will be described in detail according to a preferred embodiment.

In general, a soft plastic adhesive film is manufactured by applying a point/adhesive to a silicone release paper, heat-treating it to harden, and laminating the plastic film. Therefore, the adhesiveness and printability of the plastic film are important factors. In order to obtain a resin composition having these properties, in the present invention, an elastomer using a PBT resin and a PET copolymer as a base resin is extruded into a sheet or film state, and an adhesive or adhesive is applied to the surface to constitute a soft plastic adhesive film.

At this time, additionally, PBT resin and PET copolymer are the main raw materials, and TPEE resin, eco-friendly plasticizer, styrene-based block copolymer, acrylic rubber or butadiene rubber-based copolymer, flame retardant, filler, processing aid, It is also possible to provide the composition with a processing oil, compatibilizer, lubricant, weatherability reinforcing agent and other additives.

<Experimental Example 1>

In general, the soft PVC adhesive sheet is a soft PVC in which 40 to 60 parts by weight of a plasticizer is mixed with 100 parts by weight of PVC resin, and a film having an A hardness of 95 to 85 is mainly used. In this experiment, the physical properties of PVC, LDPE, and LLDPE resins, which are mainly used for flexible adhesive films, and this elastomer were compared and reviewed.

Physical comparison table Resin type A hardness importance Tensile strength (kgf/㎟) Elongation (%) Example 1: PVC 95±3 1.25 2.06 327 Example 2: PVC 88±3 1.23 1.78 356 Example 3: PVC 85±3 1.21 1.60 354 Example 4: PBT elastomer (Table 3 Example 1) 95±3 1.19 2.23 298 Example 5: PBT elastomer (Table 3 Example 2) 90±3 1.15 1.76 312 Example 6: PBT elastomer (Table 3 Example 3) 85±3 1.16 1.32 294 Example 7: LDPE 94±3 0.92 1.14 290 Example 8: LLDPE 96±3 0.94 1.34 184 Example 9: Olefin-based elastomer 86±3 0.89 1.89 690

(1) PBT: Sample is LG Chemical's GP1000S)

(2) LLDPE: 3120 (Hanwha Petrochemical Item No.)

(3) LDPE; 722 (Hanwha Petrochemical Item No.)

(4) Olefin-based elastomers; DOW, engage 8440.

As in Examples 1 to 9 of Table 1, the physical properties of the resins mainly used for preparing the flexible adhesive film were compared and reviewed. In general, if the film thickness is thick, a soft resin with low hardness is selected.

As a result of comparing the physical properties with reference to Examples 1 to 3 of Table 3, PBT elastomer using soft PVC and PBT resin as the base resin from Examples 1 to 6 of Table 1, the physical properties were generally similar, but when the hardness was A95 or higher, PBT The physical properties of the elastomer tend to be excellent, and when the A hardness is 90 or less, the physical properties tend to be inferior compared to that of soft PVC.

LDPE and LLDPE showed inferior physical properties compared to soft PVC or PBT elastomers, and olefinic elastomers showed superior physical properties. These test results suggest that the flexible PVC adhesive film composed of soft PVC can be replaced with a flexible adhesive film composed of PBT elastomer.

<Experimental Example 2>

Polybutylene Terephthalate (PBT) resin is made by the reaction of terephthalic acid with 1,4-butanediol. It is a crystalline resin with excellent heat resistance, chemical resistance and electrical properties among various EP (engineering plastic) resins. , It has excellent friction and abrasion resistance and dimensional safety, and is mainly used for electrical, electronic and automobile parts. In particular, it is a resin with excellent heat resistance, and the range of physical property deterioration is narrow even at high temperatures, and it can be used for a long time even at 120-130°C, and there is no deformation even under high loads.

PBT elastomer composed of PBT resin with these properties as a base resin can produce heat-resistant soft adhesive films or soft adhesive films with low shrinkage, and has the lowest processing temperature among EP resins, excellent processability, and compatibility with plasticizers It is relatively excellent, so it is easy to be flexible, and the price is also competitive at a relatively low price.

However, most EP resins are manufactured in the form of pellets, so they cannot be mixed with liquid raw materials such as plasticizers for softening, unlike PVC resins, which are powdery and porous. In the present invention, in order to solve this processing problem, a core-shell type copolymer, which is mainly used as a PVC impact reinforcing agent, was selected as an intermediate agent and a test was conducted. The core cell-type copolymer is composed of a double structure of a shell part and a core part. The cell part is mainly a resin such as acrylic or SAN resin, and the core part is made of acrylic rubber and butadiene rubber. , it is composed of rubber such as silicone rubber, and the plasticizer absorbency is good in the form of a spherical powder.

In this Experimental Example 2, an experiment was performed as shown in Table 2. ingredient Example One 2 3 4 5 6 7 8 9 10 PBT 100 100 100 100 100 100 100 100 100 100 C223A 15 15 20 20 40 80 120 160 160 240 Plasticizer (DEHCH) 30 40 40 50 80 160 240 320 320 480 TPEE 50 50 60 70 120 240 360 480 550 720 compatibility Good Good Good Good Good Good Good Good Good error miscibility Good error Good error Good Good Good Good Good Good Side Effect poor processing poor quality

(1) C223A: Misbishi Rayon's acrylic rubber copolymer (core-shell type: powder)

(2) NEO-P: Product name of Hanwha Chemical's eco-friendly plasticizer.

(3) TPEE (Thermoplastic polyester elastomer): Manufactured by Kolon Co., Ltd. Item No.: KP3340.

Soft PVC is made by mixing a plasticizer with PVC resin. The most important factor in this process is the mixability and compatibility of PVC and plasticizer. If the miscibility is poor, the processability is deteriorated, and if the compatibility is poor, the quality is poor.

Since PVC resin is powdery and porous, it is easy to absorb plasticizers. , the oil or plasticizer must be mixed by forcibly transported into the extruder using a metering pump, or mixed with a special equipment such as a kneader.

These methods result in additional equipment or a decrease in productivity. In order to solve this problem, in the present invention, an experiment using a compound line of the same method as PVC resin was conducted by selecting a powdered plastic as an intermediate material. In the experimental supermixer, from Examples 1 to 10 in Table 2, the PBT resin and TPEE resin were mixed with the acrylic rubber-based copolymer (C223A) in powder form for about 15 minutes in a mixer, and in an experimental extruder (30 mm twin-screw extruder) at 230 ° C. Mixability and compatibility were examined by extruding, pelletizing, and preparing a specimen. Example 1 had good mixability and compatibility, and had excellent physical properties as in Example 1 of Table 3.

Examples 2 and 4 of Table 2 had good physical properties, but severe cake phenomenon occurred during mixing due to excessive mixing of the plasticizer, resulting in poor processability. PVC resin has good plasticity, but PBT resin has poor plasticity compared to PVC resin, so it is possible to soften the plasticizer at a similar level to PVC resin by increasing the mixing amount of plasticizer compared to PVC resin. As a result of testing from Examples 1 to 10 in Table 2, the mixing state was good when the plasticizer content was 200% of C223A as in Examples 1 and 3, and 5 to 9. As in Examples 2 and 4, and Example 10, when the mixing amount of the plasticizer is 200% or more, the processability is deteriorated due to the viscosity (stickiness) of the mixture, and the mixing of the plasticizer in excess as in Example 10 produces a TPEE resin with excellent properties and compatibility. Even a large amount of mixing causes rapid deterioration of physical properties.

For this reason, the PBT elastomer of Example 6 in Table 1 is the cause of lower physical properties such as tensile strength and elongation compared to the PVC resin of Example 3 having the same hardness.

Unlike PVC resin, the composition mixed with PBT resin, plasticizer, and C223A has poor physical properties, so it is excellent in compatibility with these resins. A physical property reinforcement experiment was carried out by mixing.

In this experiment, the role of C223A, a butadiene rubber-based coacell-type copolymer, is a simple medium for plasticizing PBT resin by absorbing plasticizer and mixing with PBT resin. Core cell type copolymer is mainly used as an impact modifier for hard PVC resin. Because.

The core part is butadiene rubber, acrylic rubber, and silicone rubber, and the cell part mainly uses Styrene Acrylonitrile Copolymers, a copolymer made by polymerizing styrene, which is an aromatic hydrocarbon, and acrylonitrile, which is an unsaturated nitrile, for transparency and transparency. Since the silicone rubber copolymer is not compatible with the PBT resin, a butadiene rubber or acrylic rubber copolymer is mainly used in the composition of the PBT elastomer of the present invention, and the acrylic rubber copolymer is mainly used for reinforcing weather resistance. Acrylic rubber is one of the rubbers with the best weather resistance.

C223A has the best compatibility with PBT resin or PET-G resin among impact modifiers, but its compatibility is inferior to PVC resin, and as the amount of C223A mixed increases, the physical properties deteriorate.

Among EP resins, PBT resins have relatively good compatibility with plasticizers or styrene-based block copolymers, but as in Example 10, when an excessive amount of plasticizer is mixed, bleeding or blooming occurs.

The bleeding phenomenon is caused by the effect of a plasticizer or solvent, and the color of the colorant oozes out to the surface of the molded product, and the plasticizer migrates to the surface of the resin, causing stickiness or discoloration. . Blooming is a phenomenon in which the compounding agent seeps into the rubber surface and a flower pattern is drawn, which causes contamination on the surface of the resin.

Eco-friendly plasticizers are mainly ester-based plasticizers, and ester-based plasticizers are generally manufactured through an esterification reaction of an acid and an alcohol, and the ester reaction is usually carried out under an acid or metal catalyst. Due to the controversy over the toxic substances of phthalate-based plasticizers, the use of PVC resin is avoided along with environmental problems. It is a carboxylic aromatic ester that has the same plasticizing efficiency as phthalate-based plasticizers while using an ester-based material as the basic skeleton. arometic ester), benzenedicarboxylic acid ester, and diisononyl ester have been developed and their usage is rapidly increasing. Hexamol dinch plasticizer from BASF in Germany and Eco-Dehch plasticizer from Hanwha Chemical are representative eco-friendly plasticizers approved by the US FDA.

TPEE (Thermoplastic polyester elastomer) is a block copolymer composed of a hard segment (crystallizable glycol terephthalate) and a soft segment (amorphous elastomeric polytetramethylene ether terephthalate). It has excellent compatibility with other resins such as PVC, TPU, and PET-G. TPU resin also has good compatibility with PVC, PET-G, and PBT resins, but the physical properties of the composition are inferior compared to TPEE resins. As a result of the test, it has excellent compatibility with PBT resin and butadiene rubber or acrylic rubber, so it was judged as a resin suitable for improving the physical properties of elastomers based on PBT resin or PET copolymer.

The elasticity of TPEE resin is the hard segment, and the amorphous soft segment forms flexibility. The hard segment affects stiffness, modulus, mechanical strength, heat resistance, oil resistance, etc., and the soft segment affects rubber elasticity, flexibility, and low temperature characteristics. If the ratio of soft segment is high, the characteristics of elastomer such as rebound elasticity, flexibility, and impact resistance are excellent. also has a lowering effect.

<Experimental Example 3>

In order to replace the flexible PVC adhesive film with excellent physical properties and good processability, a composition having physical properties and processability equivalent to that of a soft PVC resin should be obtained. The most important factor in a composition is the compatibility between the constituent materials. In order to construct an elastomer with excellent physical properties from an elastomer based on PBT resin and PET copolymer, it is a composition using the strengths of the constituent materials. In the examples of Table 3, examples in which the compositions close to the soft PVC resin were classified by hardness centering on the hardness mainly used in the soft PVC adhesive film through the experiment were shown.

ingredient Example One 2 3 4 5 6 PBT 100 100 100 100 100 100 C223A 15 30 65 100 160 DEHCH 30 50 110 160 320 SEPS 160 white oil 240 TPEE 50 100 220 330 550 320 Hardness (A) 100±3 95±3 90±3 85±3 80±3 80±3 Tensile strength (kgf/㎟) 2.37 2.23 1.76 1.32 1.09 1.24 (Soft PVC tensile strength) (2.06) (1.78) (1.6) (1.53) (1.53) Elongation (%) 381 298 312 294 317 396 modulus 100% 1.83 198 129 90 79 56 modulus 200% 1.88 212 159 119 98 77 Injection temperature (℃) 220 220 210 200 190 220

Example of raw material composition Unit: kg

(1) C223A: Butadiene rubber-based copolymer of Misbishi Rayon (core-shell type: powder)

(2) DECH : Product name of Hanwha Chemical's eco-friendly plasticizer

(3) SEPS Strand-Based Block Copolymer

(4) Paraffin processing oil (Pprocess oil)

Table 3 exemplifies the compositions having the best physical properties for each hardness through repeated experiments in Examples 1 to 6 of the raw materials. The hardness of the most commonly used soft PVC adhesive film is A 95 to A 85, and the thickness is 0.05 mm to 0.1 mm. The tensile strength mixed with A hardness of 95±3 of Example 2 is 2.23, which is higher than the tensile strength of soft PVC compared to 2.06, and the tensile strength of hardness A90±3 of Example 3 is 1.76. The tensile strength of soft PVC of the same hardness compared to 1.76 It was similar to 1.78, but the tensile strength showed a tendency to drop, and the hardness A85±3 of Example 4 was 1.32, which was significantly different from that of the soft PVC compared to the tensile strength 1.6. As in the experiment conducted in Example 2, when the mixing amount of C223A and the plasticizer DEHCH increases, the physical properties deteriorate and, as in Example 5, the mixing amount of the TPEE resin was increased to 550 parts by weight with respect to 100 parts by weight of the PBT resin. As a result, the tensile strength was significantly improved to 1.09, but there was a big difference compared to the tensile strength of 1.53 of the soft PVC of the same hardness. As a result of this experiment, the tensile strength of soft PVC mixed with DOP as a plasticizer was stable without significant change according to the change in hardness, but the elastomer of the present invention based on PBT resin showed an unstable phenomenon.

In order to overcome this phenomenon, in Example 6, an experiment was carried out by replacing the coacell-type copolymer with a styrenic block copolymer (SBCS).

Styrene-based block copolymers have mechanical properties similar to those of most commonly used elastomers and processability like plastics.

It is divided into a hard block composed of polystrene and at least three blocks constituting a soft block with an elastomer such as polybutadiene or polyisoprene.

Styrene-based block copolymers include SBS (styrene - butadien - styrene), SEBS (styrene - ethylene - butadien - styrene), SIS (styrene - isoprene - styrene), SEPS (styrene-ethtlene-propylene-styrene), and processing oil ( As process oil), white oil, which is a paraffinic oil, is mainly used.

In this experiment, as a result of testing SEPS or white oil as a component without using C223A and DECH furnace, mechanical properties were significantly improved compared to Example 5 consisting of C223A and DECH.

SEPS is an elastomer with the best mechanical properties and oil absorption among styrenic polymers.

The mixing amount of the styrenic copolymer for lowering the hardness in the elastomer using the PET resin of the present invention and the PET copolymer as the base resin varies depending on the type of SBCS and the mixing amount of the processing oil. It is thought that it is possible to construct an eco-friendly adhesive film in which a plasticizer is not mixed, but the adhesiveness and printability are expected to be somewhat weakened.

As described above, in general, the thickness of the soft PVC adhesive film is 0.05 mm to 0.1 mm, but for a special purpose soft PVC adhesive film of 0.05 mm or less, use a soft PVC film with A hardness of 95±3 to A100±3, and a thickness of 0.1 mm or more. For soft adhesive films, films with A hardness of 85±3 to A hardness of 80±3 are generally used.

<Experimental Example 4>

ingredient Example One 2 3 4 5 PBT 100% 60% 100% 50% PET-G 30% 100% 50% C223A 25 25 25 20 20 DEHCH 50 50 50 40 40 TPEE 100 100 100 100 100 Hardness (A) 90±3 90±3 90±3 94±3 94±3 Tensile strength (kgf/㎟) 1.38 1,52 1.59 1.61 1.63 Elongation (%) 293 230 283 347 350% modulus 100% 1.06 143 149 1.25 132 modulus 200% 1.27 152 157 1.43 151 Injection temperature (℃) 220 200 190 230 200 Heat resistance (VSP): 4.6 kg/cm 2 ·°C - - - 129.2℃ 67.6℃ cold resistance - - - -53℃ or less -53℃ or less

(1)PET-G: SK Chemicals' Item No. KN100.

(2)VSP (Vicat softening temperature): ASTM D1525

<Reference> Soft PVC ; 1) Heat resistance: 65.4℃. 2) Cold resistance: -20℃

The processing temperature of PBT resin is about 230℃~240℃. Among EP resins, the processing temperature is low and processability is good, but it is relatively poor compared to PVC resin. As a result of conducting an experiment on the change of processing temperature by PET-G of the same hardness of 90±3 as in Example 3 in Example 1 of Table 4, the injection temperature dropped from 220°C to 190°C, and the workability was also good. It showed good processability similar to PVC resin, and the physical properties were rather improved. In Examples 4 and 5, as a result of comparing the heat resistance of the composition using the PBT resin as the base resin (Example 4) and the composition using the PET-G resin as the base resin (Example 5), the composition using the PBT resin as the base resin was It was superior to the composition using PET-G resin as the base resin.

PET-G resin is glycol-modified polyethylene terephthalate, which is a transparent and excellent amorphous resin copolymerized by adding CHDM (1,4-cyclohexane dimetanol) as a comonomer to improve the physical properties and processability of PET resin. It has excellent gloss, printability, impact resistance and chemical resistance, has a wide processability, does not contain environmental hormone substances, and does not generate harmful substances when incinerated. It is a resin with the best physical properties among PET copolymers as low as 190 to 200°C. The processing temperature of PBT elastomer composed of PBT resin as base resin is high at 220°C and needs to be lowered. If the processing temperature is high, productivity decreases, the defect rate increases, and energy consumption is high.

The flexible environmetally adhesive film composed of the PBT resin and PET copolymer of the present invention as described above has excellent processability, adhesion, printability, and weather resistance as well as general uses such as advertisements, furniture, stationery, crafts, and tapes. It can completely replace PVC flexible adhesive film, which is harmful to the human body and causes environmental problems, including interior materials for buildings and ships, automobile exterior materials, wallpaper, and adhesive tapes, which are rapidly increasing with better heat resistance and cold resistance than PVC resins. It has a very useful effect.

So far, the present invention has been described in detail with reference to the presented embodiments, but those of ordinary skill in the art can make various modifications and modified inventions without departing from the technical spirit of the present invention with reference to the presented embodiments. will be. The present invention is not limited by such variations and modifications, but only by the claims appended hereto.

Claims (6)

A soft eco-friendly adhesive film, characterized in that it is formed by extruding an elastomer using a PBT resin and a PET copolymer as a base resin into a sheet or film state and applying an adhesive or adhesive to the surface. The method of claim 1,
The elastomer is a soft eco-friendly adhesive film, characterized in that it is made by mixing 30 parts by weight to 320 parts by weight of an eco-friendly plasticizer and 50 parts by weight to 550 parts by weight of a TPEE (Thermoplastic copolyester elastomer) resin with respect to 100 parts by weight of the PBT resin. The method of claim 1,
PBT resin is a soft eco-friendly adhesive film, characterized in that 30% to 100% by weight is replaced with a PET copolymer resin. The method of claim 1,
A soft eco-friendly adhesive film, characterized in that 15 to 160 parts by weight of an acrylic rubber copolymer or a butadiene rubber copolymer is mixed with respect to 100 parts by weight of the PBT resin. 5. The method of claim 4,
A soft eco-friendly adhesive film characterized in that the acrylic rubber copolymer or butadiene rubber copolymer is mixed and used in an amount of 15 to 160 parts by weight of a styrenic block copolymer based on 100 parts by weight of the PBT resin. The method of claim 1,
The elastomer is a soft eco-friendly adhesive film, characterized in that the hardness is A80±3 to 100±3.